The invention relates to the production of refractory boride coatings and bodies in particular for use in cells for the electrowinning of aluminium by the electrolysis of alumina dissolved in a molten electrolyte such as cryolite or other fluoride-based electrolytes. The invention more specifically relates to a slurry for producing refractory boride coatings and bodies, as well as bodies coated with or made of refractory boride for use as components of aluminium electrowinning cells.
Aluminium is produced conventionally by the Hall-Heroult process, by the electrolysis of alumina dissolved in cryolite-based molten electrolytes at temperatures up to around 950xc2x0 C. A Hall-Heroult reduction cell typically has a steel shell provided with an insulating lining of refractory material, which in turn has a lining of carbon which contacts the molten constituents. Conductor bars connected to the negative pole of a direct current source are embedded in the carbon cathode substrate forming the cell bottom floor. The cathode substrate is usually an anthracite based carbon lining made of prebaked cathode blocks, joined with a ramming mixture of anthracite, coke, and coal tar, or with glue.
It has long been recognized that it would be desirable to make (or coat or cover) the cathode of an aluminium electrowinning cell with a refractory boride such as titanium diboride that would render the cathode surface wettable to molten aluminium which in turn would lead to a series of advantages. Many difficulties were encountered in producing refractory boride coatings which meet up to the rigorous conditions in an aluminium electrowinning cell. However, as described in the following patents, such coatings have recently been successfully introduced.
U.S. Pat. No. 5,310,476 (Sekhar et al.) discloses a method of producing a protective refractory coating on a substrate of, inter alia, carbonaceous materials by applying to the substrate a micropyretic reaction layer from a slurry containing particulate reactants in a colloidal carrier, and initiating a micropyretic reaction. The micropyretic slurry optionally also contains some preformed refractory material, and the micropyretic slurry may be applied on a non-reactive sub-layer.
U.S. Pat. No. 5,364,513 (Sekhar et al.) discloses a method of producing a protective refractory coating by applying to the substrate a reactive or non-reactive layer from a slurry containing particulate reactants and/or preformed particulate refractory materials in a colloidal carrier, and initiating a micropyretic reaction or non-reactive sintering. The colloidal carrier was selected from the group consisting of colloidal alumina, yttria, ceria, thoria, zirconia, magnesia, lithia, monoaluminum phosphate, cerium acetate and mixtures thereof. Various colloid mixtures were disclosed, such as colloidal alumina-colloidal silica and colloidal alumina-monoaluminium phosphate.
U.S. Pat. No. 5,651,874 (de Nora et al.) discloses applying a protective coating of a refractory boride such as TiB2 to a carbon component of an aluminium electrowinning cell, by applying thereto a slurry of particulate boride in a colloid in several layers with drying between each layer.
These coatings have shown outstanding performance compared to previous attempts to apply refractory coatings to components of aluminium electrowinning cells. These aluminium-wettable refractory boride coated bodies can be used in conventional cells with a deep aluminium pool and also permit the elimination of the thick aluminium pool required to partially protect the carbon cathode, enabling the cell to operate with a drained cathode.
These refractory boride coated bodies have the following attributes: excellent wettability by molten aluminium, inertness to attack by molten aluminium and cryolite, low cost, environmentally safe, ability to absorb thermal and mechanical shocks, durability in the environment of an aluminium production cell, and ease of production and processing. The boride coating also acts as a barrier to sodium penetration.
The refractory boride coated bodies find many applications on account of their excellent resistance, protection, and stability when exposed to the corrosive conditions existing in the cell even when the temperature of operation is low as in the Low Temperature electrolysis process for the production of aluminium, see for example U.S. Pat. No. 4,681,671 (Duruz).
For most applications, thin coatings (less than 1 mm thick) are required and the methods for applying such thin coatings in one or more layers from a slurry in a colloidal carrier have proven to be essentially problem-free. Nevertheless, for some special applications, for example coating certain types of drained-cathode surfaces, it would be desirable to have thicker coatings.
When, however, it was attempted to produce thicker coatings, some problems were encountered, in particular undesirable mud-cracking was found to occur in the finished, dried coating when the coating thickness exceeded about 1 mm or even only 0.8 mm depending on the coating formulation. Mud-cracking involves cracks ranging in width from 0.1 mm to 1 mm. Hairline cracks, typically less than 0.1 mm, (generally from 0.03 to 0.09 mm) are also formed but are more acceptable. Despite this problem of mud-cracking as the thickness increases, the coatings of U.S. Pat. No. 5,651,874 (de Nora et al) remain outstandingly the best available industrially-applicable coatings.
In WO 97/08114 (Sekhar et al.) it has been proposed to make bodies of refractory boride, for example by slip casting or pressing a slurry of particulate boride in a colloid.
The invention sets out to improve the production of refractory boride coatings or bodies for use as cell components for aluminium electrowinning cells, especially for use as cathodes.
One object of the invention is to provide an improved slurry for the production of bodies or coatings of refractory boride.
Another object of the invention is to produce refractory boride coated bodies and refractory boride bodies starting from readily available and relatively inexpensive commercial particulate borides or their precursors in a specific colloidal carrier.
A specific object of the invention is to produce bodies coated with refractory borides with coating thicknesses equal to or greater than those previously possible, without mud-cracking, the coatings being aluminium-wettable and electrically conductive So they can serve as coatings for cathodes or other cell components of aluminium production cells.
In the production of xe2x80x9cthickxe2x80x9d refractory boride coatings, it has been discovered that the mud-cracking problem can be alleviated by utilizing specific colloidal carriers. Moreover, it has been observed that these specific colloidal carriers are also advantageous when producing normal xe2x80x9cthinxe2x80x9d coatings and even more advantageous when producing bodies of refractory borides, as opposed to coatings.
According to one main aspect of the invention, a slurry for the production of bodies or coatings of refractory boride comprises particulate preformed refractory boride and/or particulate precursors of refractory boride in a colloidal carrier which comprises colloidal particles with a non-gaussian particle size distribution, comprising at least two distinct fractions of colloidal particles having mean particle sizes which differ from one another.
In contrast to the known colloid mixtures of different colloidal components (colloidal alumina and colloidal silica, for example) this colloidal carrier according to the invention is obtainable by mixing two different xe2x80x9cgradesxe2x80x9d of the same colloid, producing a desirable particle size distribution.
xe2x80x9cGradexe2x80x9d is to be understood as the mean particle size of the colloidal particles, with at least 50% of the particles of that particular particle size. Commercially available colloids have a predominant particle size with generally gaussian particle size distribution.
Use of this bi- or multigrade colloidal carrier, advantageously in combination with an organic additive, provides an unexpected combination of properties, namely better homogeneity/bonding without cracking and enhanced protection against sodium penetration when the coating or body is used as a component in an aluminium production cell. Moreover, the slurry with this mixed colloidal carrier has improved thixotropic properties, in particular it remains in suspension much longer than standard colloids, which leads to significant cost savings. The thixotropic mix minimizes sedimentation of the refractory boride powders and the aged dispersion does not result in dense sediments. The slurry with the mixed colloid thus remains stable, providing increased shelf life, while remaining easy to apply, for example by brushing. Surprisingly, use of the modified colloidal carrier also leads to a lowering of the resistivity of the coating or body, thereby increasing the cell efficiency.
It should be noted that mixing of different types of colloids is not normally to be recommended because physical and chemical reactions may take place resulting in coagulation, flocculation, rise in pH or irreversible gelation, In the colloid mixture according to the invention, one colloid will generally be of the polymeric type, and the other non-polymeric.
Usually, two distinct fractions of colloidal particles have mean particle sizes which differ from one another by 10-50 nanometers, and the slurry can include a first fraction of colloidal particles with a mean particle size in the range 5-50 nanometers (e-g. 10-30 nanometers), and a second fraction of colloidal particles with a mean particle size in the range 30-100 nanometers (e.g. 40-60 nanometers). This slurry optionally further includes a third distinct fraction of colloidal particles with a mean particle size in the range 100-250 nanometers.
The first and second particle fractions of the slurry can be in a volume ratio from 10:6 to 10:16, for example from 10:8 to 10:14 or more particularly from 10:10 to 10:12, i.e. by volume of the colloids in the mixture.
In another aspect, the slurry according to the invention comprises 30-50 volume % of colloids with a mean particle size less than 20-40 nanometers and 70-50 volume % of colloids with a mean particle size greater than 20-40 nanometers. For example the colloid can contain 30-50 volume%, say about 40 volume %, of colloids with a mean particle size less than about 30 nanometers and 70-50 volume %, say about 60 volume % of colloids with a mean particle size greater than about 30 nanometers.
In advantageous embodiments, the colloids contain particle fractions wherein the largest fraction has a mean diameter of 60 nanometres, or even 50 nanometres Such colloids contain a large spread of particles with diameters less than 50 nanometres.
The slurry""s colloidal carrier is usually selected from the group consisting of colloidal alumina, yttria, ceria, thoria, zirconia, magnesia, lithia, monoaluminum phosphate, cerium acetate and mixtures thereof. Normally, however, the colloidal particles of the colloidal carrier are all particles of the same colloid. It is surprising that a mixture of one colloid, say colloidal alumina, obtainable by mixing together two grades of colloidal alumina with different mean particle sizes, is advantageous compared to the individual grades.
The colloidal carrier is usually in an aqueous medium but, advantageously, the slurries of the present invention also include at least one organic additive selected from the group consisting of polyvinyl alcohol, polyethylene glycol, ethylene glycol, polyacrylic acid, hydroxy propyl methyl cellulose, butyl benzyl phthalate and aluminium polymethacrylate.
The colloid may be derived from colloid precursors and reagents which are solutions of at least one salt such as chlorides, sulfates, nitrates, chlorates, perchlorates or metal organic compounds such as alkoxides, formates, acetates of aluminium, silicon, yttrium, cerium, thorium zirconium, magnesium and lithium. These colloid precursors or colloid reagents can contain a chelating agent such as acetyl acetone or ethylacetoacetate. The aforesaid solutions of metal organic compounds, principally metal alkoxides, can be of the general formula M(OR)z where M is a metal or complex cation, R is an alkyl chain and z is a number, preferably from 1 to 12.
It is also possible to include further components in the colloidal slurry, for example powdered aluminium which improves the conductivity of the resulting coating or body.
The pre-formed particulate refractory boride is usually selected from borides of titanium, chromium, vanadium, zirconium, hafnium, niobium, tantalum, molybdenum and cerium The preferred particulate refractory boride is titanium diboride.
When choosing the refractory boride powder, the particle size selection is of some importance. It is preferable to choose particle size below 100 micrometers and to choose particle sizes which are varied For example it is preferable to choose particle sizes extending over a range where the smallest particles are at least two times and preferably at least three times smaller than the large ones. Generally, the ratio of the particle sizes will be in the range from 2:1 to 15:1, usually from about 3:1 to 10:1, for instance a ratio of about 3:1 with large particles in the range 15 to 30 micrometers and small particles in the range 5 to 10 micrometers, or a ratio of about 10:1 with large particles in the range from 30 to 50 micrometers and small particles in the range from 3 to 5 micrometers. Usually, the preformed particulate metal boride has particles with sizes in the range from about 3 micrometers to about 50 micrometers.
It has been ascertained that the choice of the particle size of the metal boride influences the maximum thickness obtainable without mud-cracking and, for all types and mixtures of the refractory boride, use of the mixed colloidal carrier according to the invention increases the maximum obtainable thickness without mud-cracking. Mud-crack-free coatings up to 4, 6 or even 8 mm thick can thus be achieved.
The slurry usually contains 5-100 g of the pre-formed particulate refractory boride per 10 ml of colloid and each colloid has a dry colloid content corresponding to up to 50 weight % of the colloid plus liquid carrier, preferably from 5 to 30 weight %, the optimum being from 7-20 weight %.
According to the invention, there is provided a method of applying a refractory boride to a component of a cell for the production of aluminium by the electrolysis of alumina dissolved in a cryolite-based molten electrolyte, to protect the component from attack by liquid and/or gaseous components of the electrolyte in the form of elements, ions or compounds, the method comprising applying to the surface of the component the previously described mixed bi- or multigrade slurry and drying the coated surface. All previously-described features of the slurry are applicable in the method, such as the inclusion of an organic additive.
The invention also provides a method of producing a body coated with a refractory boride from the group consisting of the borides of titanium, chromium, vanadium, zirconium, hafnium, niobium, tantalum, molybdenum and cerium. The coating according to the invention includes a refractory boride containing a specific grade of colloidal binder or preferably at least two colloids, selected from the group consisting of colloidal alumina, silica, yttria, ceria, thoria, magnesia, lithia, monoaluminium phosphate and cerium acetate, each said colloid having a different grade, and is obtained from a slurry of particulate refractory boride in one or more of said colloids, by forming and drying the slurry.
Drying of the slurry is followed by heat treatment before or after the component is installed in an aluminium production cell.
The slurry is usually applied in several layers, for example by brushing, by roller or spraying, each layer being allowed to dry at least partially in the ambient air or assisted by heating before applying the next layer, followed by a final heat treatment to dry the slurry after application of the last layer. Heating at a temperature from 80 to 300xc2x0 C. can for example be carried out each time an added thickness of about 0.2 to about 0.6 mm is reached by the application of one or more layers.
The resulting coating of refractory boride usually has a dried thickness up to 8.0 mm without mud-cracking.
Another aspect of the invention is a method of producing a self-sustaining body of a refractory boride preferably from the group consisting of the borides of titanium, chromium, vanadium, zirconium, hafnium, niobium, tantalum, molybdenum and cerium, in which the body includes a refractory boride and a colloid preferably from the group consisting of colloidal alumina, silica, yttria, ceria, thoria, zirconia, magnesia, lithia, monoaluminium phosphate and cerium acetate, and is obtained from the previously-described slurry of the invention containing preformed refractory boride, by forming and drying the slurry.
For example, the slurry is cast into a die or mold on a porous layer and the cast slurry is allowed to dry by draining the liquid through the porous layer. Further methods of forming bodies of refractory boride from slurries are disclosed in WO 97/08114 (Sekhar et al.).
To assist rapid wetting by molten aluminium, the bodies made of or coated with refractory borides may be exposed to molten aluminium in the presence of a flux. assisting penetration of aluminium into the refractory boride, the flux for example comprising a fluoride, a chloride or a borate, of at least one of lithium and sodium, or mixtures thereof. Such treatment favors aluminization of the surface of the body by the penetration therein of aluminium.
The invention also applies to methods of producing bodies or coatings from a slurry according to the invention which contains, instead of or in addition to particulate preformed refractory boride, precursor powders which react to form the refractory boride(s). For instance titanium and boron powders can be reacted in the presence of preformed titanium diboride which moderates the reaction.
Numerous examples of micropyretic reaction mixtures for this purpose are described in the aforementioned U.S. Pat. Nos. 5,310,476 and 5,364,513 (both Sekhar et al.), the disclosures whereof are incorporated herein by way of reference.
The invention also concerns cell components of aluminium production cells, in particular those which in use of the cell are exposed to contact with molten cryolite and/or molten aluminium. The cell component is for instance a cathode or forms part of a cathodic cell bottom, or may be a tile or a component such as a weir or a baffle or grid immersed in the molten aluminium.
According to the invention, there is provided a component of a cell for the production of aluminium by the electrolysis of alumina dissolved in a cryolite-based molten electrolyte, which cell component is subjected to molten cryolite and/or to molten aluminium. The cell component comprises a body or a coating made from the slurry of the present invention.
In the case of components coated with the refractory boride, the main body or substrate of the component will often be made of carbon or of a carbon-containing composite. It is also possible to coat refractory substrates, such as various types of alumina or other refractory oxycompounds as well as composite materials comprising an electrically conductive and an electrically non-conductive component.
For example, a body can be made including titanium diboride as the reaction product of titanium oxide, boron oxide and aluminium from a slurry according to the invention and/or coated with a refractory boride such as titanium diboride by the method of the invention.
Usually, the component will have a porous surface, which is the case for carbon, but coatings can also be applied successfully to essentially impervious substrates.
The component may be a current-carrying component for example a cathode, a cathode current feeder, or the cathodic part of a bipolar electrode. Particular advantages are achieved for drained cathodes where the produced aluminium continuously drains from the cathode surface which is a made of refractory boride or coated with a relatively thick and crack-free coating of refractory boride according to the invention.
The bodies may consist of blocks or tiles that can be fitted together to form a cell bottom of an aluminium production cell, which acts to carry current to the cathodic pool if there is one, or to a thin layer of aluminium in drained cells, or they may form a packed bed of bodies on a cell bottom.
The component advantageously forms part of a cathode through which the electrolysis current flows, the refractory boride cathodic surface being in contact with the cathodically-produced aluminium. For example, it is part of a drained cathode wherein the refractory boride forms the cathodic surface on which the aluminium is deposited cathodically, the component""s drained surface being arranged usually upright or at a slope to assist draining of the aluminium. Arrangements with a horizontal drained surface are also possible.
For example, providing a xe2x80x9cthickxe2x80x9d and crack-free refractory boride coating according to the invention is very advantageous when applied to a drained-cathode grid as described in U.S. Pat. No. 5,472,578 (de Nora)
The invention also relates to an aluminium electrowinning cell comprising a cell component including a body or coating as discussed above as well as a method of producing aluminium using such cells and methods of operating the cells.
Such cells may comprise a component which in operation of the cell is exposed to molten cryolite or aluminium, said component including a body or coating as discussed above, wherein the product aluminium is in contact with the refractory boride, which may be a cathode or form part of a cathodic cell bottom
A method of operating the cells comprises producing a cell component which includes a body or a coating made from a slurry as described above; optionally subjecting the coated component to heat treatment; placing the component in the cell so that it will be contacted by the cathodically produced aluminium, and/or the molten electrolyte; and operating the cell to produce molten aluminium.
As mentioned previously, in the case of cell components coated with the refractory boride, the main body or substrate of the component can be made of carbon or of a carbon-containing composite or a refractory material as well as composite materials comprising an electrically conductive and an electrically non-conductive component.
Advantageously, the cell includes a component comprising a body including titanium diboride as the reaction product of titanium oxide, boron oxide and aluminium using a slurry according to the invention and/or coated with a refractory boride by the method of the invention.
The cell component may be a current-carrying component for example a cathode, in particular a drained cathode.
Operation of the cell can be at normal operating temperatures (about 950xc2x0 C.) or in a low temperature process, with the molten fluoride-based electrolyte containing dissolved alumina at a temperature below 900xc2x0 C., usually at a temperature from 680xc2x0 C. to 880xc2x0 C. The low temperature electrolyte may be a fluoride melt or a mixed fluoride-chloride melt. This low temperature process is operated at low current densities on account of the low alumina solubility.